Reaction product of alkanolamine and two particular acids

ABSTRACT

Reaction product formed by the condensation of alkanolamine, polyhalopolyhydropolycyclicdicarboxylic acid or derivative and aliphatic substituted dicarboxylic acid. The reaction product has utility as a stabilizer against deterioration of organic substances, such as lubricants, hydrocarbon oils and plastics, as well as utility as a detergent, dispersant, extreme pressure additive, flame retardant and also possessing insecticidal properties.

United States Patent Cyba [4 1 June 6,1972

[54] REACTION PRODUCT OF ALKANOLAMINE AND TWO PARTICULAR ACIDS [72] Inventor:

[73] Assignee:

Henryk A. Cyba, Evanston, Ill.

Universal Oil Products Company, Des Plaines, Ill.

[22] Filed: Mar. 23, 1970 [21] Appl. No.: 22,010

Related US. Application Data [63] Continuation-impart of Ser. No. 720,339, Apr. 10, 1968, Continuation-impart of Ser. No. 329,979, Dec. 12, 1963, abandoned.

[52] US. Cl. ..260/485 H, 252/8. 1, 252/37.2, 252/49.6, 252/5 1.5 A, 252/57, 252/390, 252/392,

252/396, 260/45.85, 260/75 N, 78 TF/, 260/78 VA,

[51] Int. Cl ..C07c 93/16 [58] field ofSearch ..260/485 G, 485 J, 485 H [56] References Cited UNITED STATES PATENTS 3,499,905 3/1970 Koch et a1 ..260/294.3

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Robert Gerstl Attorney-James R. Hoatson, Jr. and Bernard 1... Kramer [57] ABSTRACT 20 Claims, No Drawings REACTION PRODUCT OF ALKANOLAMINE AND TWO PARTICULAR ACIDS CROSS REFERENCE TO RELATED APPLICATIONS This is a continuation-in-part of copending application Ser. No. 720,339, filed Apr. 10, 1968, which is a continuation-inpart of application Ser. No. 329,979, filed Dec. 12, 1963, and now abandoned.

BACKGROUND OF THE INVENTION In the parent applications referred to above, novel compositions of matter comprising the reaction products of a particw lar type of carboxylic acid or derivative thereof with an alkanolamine are disclosed. These novel compositions of matter possess utilities as set forth in the preceding abstract.

DESCRIPTION OF THE INVENTION Included in the novel compositions of matter disclosed in the applications referred to above are the condensation products of the polyha1opolyhydropolycyclicdicarboxylic acid or derivative, alkanolamine and aliphatic substituted dicarboxylic acid as exemplified by dodecenyl succinic anhydride. The present application is directed to these reaction products as novel compositions of matter and to the use thereof as addi tives.

In one embodiment the present invention relates to the reaction product formed by the condensation at a temperature of from about 175 F. to about 500 F. and for a time of from about one-half to about 40 hours of (a) one mole proportion of a polyhalopolyhydropolycyclicdicarboxylic acid as hereinafter defined, corresponding anhydride, corresponding die] or ester of said acid, (b) l to 2 mole proportions of an alkanolamine as hereinafter defined and (c) l to 2 mole proportions of a dicarboxylic acid particularly an aliphatic substituted dicarboxylic acid containing from about four to about 80 carbon atoms in said aliphatic or corresponding anhydride.

In another embodiment the present invention relates to the use of the reaction product as an additive in organic substances including hydrocarbon oil and particularly lubricants, as well as grease. In another embodiment it is used as an additive in plastics, textiles, etc. requiring flame proofing proper- As hereinbefore set forth, the reaction product of the present invention is prepared by using a polyhalopolyhydropolycyclicdicarboxylic acid or derivative as a reactant. In a preferred embodiment the acid or anhydride thereof is used. Any suitable acid or anhydride meeting these requirements is used in accordance with the present invention. In one embodiment the acid or anhydride is of the type known in the art as Chlorendic" or HET acid or anhydride. This acid is prepared by the Diels-Alder addition reaction of maleic acid and hexachlorocyclopentadiene or more conveniently by the reaction of maleic anhydride and hexachlorocyclopentadiene to form the corresponding anhydride and then hydrolyzed to form the acid. The corresponding anhydride is prepared by the reaction of maleic anhydride and hexachlorocyclopentadiene. This acid or anhydride also may be named l,4,5,6,7,7-hexachlorobicyclo-( 2.2.1 )-5-heptene-2,3-dicar boxylic acid or the corresponding anhydride. These compounds are prepared by the reaction of equal molar quantities of the reactants, generally by refluxing preferably at about 350 F. in the presence of a solvent. These reactions are well known in the art and are described, for example, in U.S. Pat. No. 2,606,910 and elsewhere.

In place of maleic acid or maleic anhydride, it is understood that other suitable dicarboxylic acids containing carbon to carbon unsaturation may be employed. Illustrative examples include fumaric acid, itaconic acid, citraconic acid, glutaconic acid, etc. Also, in place of hexachlorocyclopentadiene, other suitable halo-substituted cycloalkadienes may be used. Illustrative examples include 1,2-dichlorocyclopentadiene, 1,5- dichlorocyclopentadiene, l,2,3-trichlorocycIopentadiene,

1,2,3,4-tetrachlorocyclopentadiene, l,2,3,4,5-pentachlorocyclopentadiene and similar compounds in which all or part of the chlorine is replaced by other halogen and particularly hydrolyzing the formed A anhydride to the'A" acid. The

bromine.

A particularly preferred polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is prepared by the Diels-Alder condensation of a conjugated aliphatic diene with an olefinic dicarboxylic acid and then further condensing the resultant cyclohexenedicarboxylic acid with a halocycloalkadiene. A specifically preferred reaction product is the Diels-Alder condensation of l,3-butadiene with maleic anhydride to form l,2,3,6-tetrahydrophthalic anhydride, followed by the Diels Alder condensation with hexachlorocyclopentadiene. The product may be named 5,6,7,8,9,9-hexachlorol,2,3,4,4a,5,8,8-octahydro-5,8-methano-2,3- naphthalenedicarboxylic anhydride, hereinafter referred to as A" anhydride. The corresponding acid is prepared preferably by starting with maleic anhydride as above and acid may be named 5,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalene-dicarboxylic acid, hereinafter referred to as A acid. Here again, other conjugated aliphatic dienes may be used including, for example, 2- methyl-1,3-butadiene, 1,3-pentadiene, l,3-hexadiene, 2,4- hexadiene, 2,3-dimethyl-l,3-butadiene, 1,3,-heptadiene, 2,4- heptadiene, conjugated nonadienes, etc. halodienes as, for example, chloroprene and particularly lchlorobutadiene and 1,4-dichlorobutadiene. Similarly, other unsaturated dicarboxylic acids may be used including fumaric acid, itaconic acid, citraconic acid, glutaconic acid, mesaconic acid, etc. Also, other halocycloalkadienes may be used including, for example, those specifically hereinbefore set forth. The preparation of these compounds also is known in the art and is set forth in detail in US. Pat. No. 3,017,431.

Still another preferred polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is prepared by condensing cyclopentadiene with maleic acid or maleic anhydride to form norborn- 5-ene-2,3-dicarboxylic acid or anhydride and then condensing the same with hexachlorocyclopentadiene. The product may be named 5,6,7,8,9,9-hexachloro- I ,2,3,4,4a,5,8,8a-octahydrol ,4,5,8-dimethano-2,B-naphthalenedicarboxylic acid or anhydride, hereinafter referred to as 8" acid an 8" anhydride respectively. Here again, it is understood that other conjugated cycloaliphatic dienes, other unsaturated dicarboxylic acids or anhydrides and other polyhalocycloalkadienes may be used to prepare suitable polyhalopolyhydropolycyclicdicarboxylic acids or anhydrides.

From the above, it will be seen that any suitable polyhalopolyhydropolycyclicdicarboxylic acid or anhydride may be used in accordance with the present invention. The polyhalopolyhydropolycyclicdicarboxylic acid may be illustrated by the following structure:

in which X is selected from the group consisting of halogen and particularly chlorine and/or bromine, hydrogen and an alkyl radical of from 1 to l0 and preferably from one to four carbon atoms, at least two of the Xs being halogen, Y is selected from the group consisting of halogen, hydrogen and an alkyl radical of l to 10 and preferably from one to four carbon atoms,m is

an integer offrom l to 4, n ranges from 0 to 4 and p ranges from 0 to 4.

The above structure illustrates the dicarboxylic acid. In the interest of simplicity, the corresponding anhydride is not being illustrated, but is readily ascertainable from the above structure.

Referring to the above structure, when X is chlorine, m is l, n is O and p is O, the compound is l,4,5,6,7,7 hexach1orobicyclo-( 2.2.1 )-5-heptene-2,3-dicarboxylic acid or the corresponding anhydride. Similarly, when X is chlorine, m is 1, n is 0 and p is l, the compound is 5,6,7,8,9,9-hexachlorol,2,3,4,4a,5,8,8a-octahydro-5 ,8-methano-2,3- naphthalenedicarboxylic acid or the corresponding anhydride.

Also, when X is chlorine, Y is hydrogen, m is l, n is l and p is l, the compound is 5,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8aoctahydrol ,4,5 ,8-dimethano-2,3-naphthalenedicarboxylic acid or the corresponding anhydride.

While the particular acid or anhydride set forth above is preferred, it is understood that an ester of the acid may be used for reacting with the alkanolamine. Any suitable ester may be used and is prepared by reacting the acid or anhydride with an alcohol under conditions to liberate water. While the alcohol may contain from one to 18 carbon atoms, it preferably contains one to four carbon atoms. Illustrative alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, etc.

In still another embodiment the corresponding mono or diol of the dicarboxylic acids set forth above may be used. The diol is readily prepared by reacting hexachlorocyclopentadiene with l,4-butenediol. In another example, the diol is prepared by reacting hexachlorocyclopentadiene with alphaallyl glycerol ether: These reactions are well known in the an and are described, for example, in US. Pat. No. 3,007,958. Similarly, hexachlorocyclopentadiene is reacted with 2,3- dimethanolcyclohex-S-ene to form the diol corresponding to the A acid. It is understood that any suitable mono or diol of the dicarboxylic acid set forth above may be used.

As hereinbefore set forth another reactant is an alkanolamine. In one embodiment the alkanolamine comprises a monoalkanolamine, preferably containing from two to 20 carbon atoms including ethanolamine, propanolamine, butanolamine, pentanolamine, hexanolamine, heptanolamine, octanolamine, nonanolamine, decanolamine, undecanolamine, dodecanolamine, tridecanolamine, tetradecanolamine, pentadecanolamine, hexadecanolamine, heptadecanolamine, octadecanolamine, nonadecanolamine, eicosanolamine, etc., and particularly these alkanolamines in which one or both of the amino hydrogens is replaced by an alkyl group, the alkyl group containing from one to 50 and preferably from one to 20 carbon atoms. Illustrative substituted alkanolamines include N-methyl-ethanolamine, N- ethyl-ethanolamine, N-propyl-ethanolamine, N-butylethanolamine, N-pentyl-ethanolamine, N-hexylethanolamine, N-heptylethanolamine, N-octyl-ethanolamine, N-nonyl-ethanolamine, N-decyl-ethanolamine, N-undecylethanolamine, Ndodecylethanolamine, Ntridecylethanolamine, N-tetradecyl-ethanolamine. N-pentadecylethanolamine, N-hexadecyl-ethanolamine, N-heptadecylethanolamine, N-octadecylethanolamine, N-nonadecylethanolamine, N-eicosyl-ethanolamine,etc., N,N- dimethylethanolamine, N,N-diethyl-ethanolamine, N,N- dipropyl-ethanolamine, N,N-dibutyl-ethanolamine, N,N- dipentyl-ethanolamine, N,N-dihexyl-ethanolamine, N,N-

diheptyl-ethanolamine, N,N-dioctyl-ethanolamine, N,N-dinonyl-ethanolamine, N,N-didecylethanolamine, N,N-diundecylethanolamine, N,N-didodecylethanolamine, N,N-ditridecylethanolamine, N,N-ditetradecylethanolamine, N,N-dipentadecyl-ethanolamine, N,N-dihexadecylethanolamine, N,N- diheptadecyl-ethanolamine, N,N-dioctadecylethanolamine, N,N-dinonadecyl-ethanolamine, N,N-dieicosylethanolamine, etc., as well as similarly substituted alkanolamines in which the alkanol moiety contains from three to twenty carbon atoms. It is understood that the alkanolamines may contain an aliphatic substituent attached to one or more of the carbon atoms forming the alkanol group. Furthermore, it is understood that a mixture of the alkanolamines may be used, preferably being selected from those hereinbefore set forth, and also that the substitution may comprise cycloalkyl and particularly cyclohexyl.

In another and preferred embodiment, the alkanolamine contains at least two hydroxyl groups and one amino group or at least one hydroxyl group and two amino groups. The use of such alkanolamines results in a polymer formation, although under some conditions monomeric simple derivatives may be formed instead of polymers. The embodiment of the alkanolamine containing two hydroxyl and one amino groups are dialkanolamines and preferably N-aliphatic-dialkanolamines in which the aliphatic group attached to the nitrogen atom contains from one to about 50 carbon atoms and preferably from about eight to about 22 carbon atoms. In a particularly preferred embodiment, the aliphatic group contains from one to about 20 carbon atoms each. The alkanol groups preferably contain from about two to about four carbon atoms each, although it is understood that they may contain up to about twenty carbon atoms each. Preferably the N- aliphatic-dialkanolamine is an N-alkyl-diethanolamine. Illustrative compounds include N-methyl-diethanolamine, N-

ethyl-diethanolamine, N-propyl-diethanolamine, N-nonyldiethanolamine, N-decyl-diethanolamine, N-undecyldiethanolamine, N-dodecyl-diethanolamine, N-tridecyldiethanolamine, N-octatetracontyl-diethanolamine, N- nonatetracontyl-diethanolamine, N-pentacontyldiethanolamine, etc. In some cases, N-alkenyldiethanolamines may be utilized. Illustrative N-alkenyldiethanolamines include N-hexenyl-diethanolamine, N-heptenyl-diethanolamine, N-octenyl-diethanolamine, N-undecenyldiethanolamine, N-dodecenyl-diethanolamine, N-tridecenyldiethanolamine, N-tetradecenyl-diethanolamine, N-pentadecenyl-diethanolamine, N-heXadecenyl-diethanolamine, N-heptadecenyl-diethanolamine, N-octadecenyldiethanolamine, N-nonadecenyl-diethanolamine, N-eicosenyl-diethanolamine, etc.

It is understood that the N-aliphatic-diethanolamines may contain an aliphatic substituent attached to one or both of the carbon atoms forming the ethanol groups.'These compounds may be illustrated by N-aliphatic-di-( l-methylethanolamine), N-aliphatic-di-( l-ethyl-ethanolamine), N-aliphatic-di-( 1- propyl-ethanolamine), N-aliphatic-di-( l-butyl-ethanolamine N-aliphatic-di-( l-pentyl-ethanolamine), N-aliphatic-di-( 1- hexyl-ethanolamine etc., N-aliphatic-di-( 2-methylethanolamine), N-aliphatic-di-(Z-ethyI-ethanolamine), N- aliphatic-di-( 2-propyl-ethanolamine N-aliphatic-di-( 2-butylethanolamine), N-aliphatic-di-(Z-pentyI-ethanolamine), N- a.liphatic-di-(2-hexyl-ethanolamine), etc. It is understood that these specific compounds are illustrative only and that other suitable compounds containing the diethanolamine configuration may be employed.

The specific compounds hereinbefore set forth are examples of N-aliphatic diethanolamines. Other N-aliphaticdialkanolamine include N-aliphatic-dipropanolamines and N- aliphatic-dibutanolamines, although N-aliphatic-dipentanolamines, N-aliphatic-dihexanolamines and higher dialkanolamines may be used in some cases. It is understood that these dialkanolamines may be substituted in a manner similar to that specifically described hereinbefore in connection with the discussion of the diethanolamines. Furthermore, it is understood that mixtures of N-aliphatic-dialkanolamines may be employed, preferably being selected from those hereinbefore set forth, and also that the substitution may comprise cycloalkyl and particularly cyclohexyl. Also, it is understood that the various dialkanolamines are not necessarily equivalent.

A number of N-alkyl-diethanolamines are available commercially and are advantageously used in preparing the condensation product. For example, N-tallow-diethanolamine is available under the tradename of Ethomeen T/12." This material is a gel at room temperature, has an average molecular weight of 354 and a specific gravity at 25/25 C. of 0.916. The alkyl substituents contain from about 12 to carbon atoms per group and mostly 16 to 18 carbon atoms. Another mixed product is available commercially under the tradename of Ethomeen S/ 12 and is N-soya-diethanolamine. It is a gel at room temperature, has an average molecular weight of 367 and a specific gravity at /25 C. of 0.911. The alkyl substituents contain 16 to 18 carbon atoms per group. Still another commercial product is Ethomeen C/ 12, which is N- coco-diethanolamine, and is a liquid at room temperature, and

has an average molecular weight of 303 and a specific gravity at 25/25 C. of 0.874. The alkyl groups contain mostly 12 carbon atoms per group, although it also contains groups having from eight to 16 carbon atoms per group. Still another commercially available product is N-stearyl-diethanolamine, which is marketed under the tradename of Ethomeen 18/12. This product is a solid at room temperature, has an average molecular weight of 372 and a specific gravity at 25/25C. of 0.959. It contains 18 carbon atoms in the alkyl substituent.

When the alkanolamine contains one hydroxyl and two amino groups, a preferred alkanolamine is aminoalkyl alkanolamine. The alkanolamine preferably contains from four and preferably from six to about 50 carbon atoms. Illustrative compounds include aminoethyl ethanolamine, aminoethyl propanolamine, aminoethyl butanolamine, aminoethyl pentanolamine, aminoethyl hexanolamine, etc., aminopropyl ethanolamine, aminopropyl propanolamine, aminopropyl butanolamine, aminopropyl pentanolamine, aminopropyl hexanolamine, etc., aminobutyl ethanolamine, aminobutyl propanolamine, aminobutyl butanolamine, aminobutyl pentanolamine, aminobutyl hexanolamine, etc., aminopentyl ethanolamine, aminopentyl propanolamine, aminopentyl butanolamine, aminopentyl pentanolamine, aminopentyl hexanolamine, etc., aminohexyl ethanolamine, aminohexyl propanolamine, aminohexyl butanolamine, aminohexyl pentanolamine, aminohexyl hexanolamine, etc. Here again, one or both of the nitrogen atoms of the aminoalkyl alkanolamine may contain hydrocarbon substituents and particularly alkyl group of groups of from one to about 50 and preferably of from one to 20 carbon atoms each or cycloalkyl groups and particularly cyclohexyl or mixtures thereof.

As hereinbefore set forth another reactant is a dicarboxylic acid and particularly an aliphatic substituted dicarboxylic acid containing from about two to 80 carbon atoms in said aliphatic, or the corresponding anhydride. In one embodiment the aliphatic substituent is an alkenyl group and the preferred reactant comprises an alkenyl acid anhydride, as, for example, dodecenyl-succinic anhydride. Other alkenyl acid anhydrides include butenyl-succinic anhydride, pentenyl-succinic anhydride, hexenyl-succinic anhydride heptenyl-succinic anhydride, octenyl-succinic anhydride, nonenyl-succinic anhydride, decenyl-succinic anhydride, undecenyl-succinic anhydride, tridecenyl-succinic anhydride, tetradecenyl-succinic anhydride, pentadecenyl-succinic anhydride, hexadecenylsuccinic anhydride, heptadecenyl-succinic anhydride, octadecenyl-succinic anhydride, nonadecenyl-succinic anhydride, eicosenyl-succinic anhydride and higher molecular weight alkenyl-succinic anhydrides.

When utilized in lubricating oil or other high boiling substrate, the alkenyl substituent preferably contains from 40 to 80 or more carbon atoms. These high molecular weight reactants contribute favorably to the solubility of the reaction product in the lubricating oil or other heavy substrates. The higher molecular weight alkenyl-acid anhydrides are prepared in any suitable manner and conveniently by reacting a high molecular weight polyolefin with maleic anhydride. The polyolefins are exemplified by the polymerization of ethylene, propylene, l-butene, Z-butene, isobutene, pentene or mixtures thereof. The polyolefins preferably have a molecular weight of from about 700 to about 1,400. The preparation of the polyolefins is well known in the art and a number of thereof are available commercially. Accordingly such details of preparation are not necessary in the present application. Similarly, the reaction of the polyolefin with maleic anhydride is also well known in the prior art and in fact a number of these are available commercially. in general the preparation of the alkenyl-succinic anhydride is effected at a temperature of from about 300 to about 500 F. by reacting maleic anhydride with the olefinic polymer in a mole ratio of about 1:1 to about 5:1 respectively. As mentioned above, the preparation of the high molecular weight alkenyl-acid anhydride is well known and need not be described in detail herein.

While the alkenyl-succinic anhydrides are preferred, it is understood that the alkyl-succinic anhydrides may be employed, the alkyl groups containing from about four to about carbon atoms and preferably corresponding to the alkenyl groups hereinbefore set forth. Similarly, while the aliphaticsuccinic anhydrides are preferred, it is understood that the aliphatic substituted anhydride of other acids may be employed including, for example, aliphatic adipic anhydrides, aliphatic glutaric anhydrides, aliphatic pimelic anhydrides, aliphatic suberic anhydrides, etc.

The aliphatic substituted dicarboxylic acid is particularly preferred for use in the preparation of a composition designed for use in oils. However, plastics and polymers, such as rubber, ABS, acrylates, polystyrene, polyesters, polyvinyls, polyolefins, etc; unsaturated non-substituted dicarboxylic acids or polycarboxylic acids may be preferred. Illustrative acids include fumaric acid, itaconic acid, citraconic acid, glutaconic acid, etc., corresponding anhydrides and especially maleic acid and more particularly maleic anhydride.

The derivatives prepared from the unsaturated dibasic acid, alkanolamine and polyhalopolyhydropolycyclicdicarboxylic acid or anhydride, by virtue of the unsaturated introduced via the unsaturated or polymerizable double bond present in the acid are able to crosslink, copolymerize or graft with the basic polymer, resin, rubber or coating. This is especially useful in imparting flame retarding properties to the polymer, rubber or coating. The composition of the present invention thus is able to coreact or copolymerize with the substrate and yield a product in which the flame retardant of the present invention is an integral part and cannot be washed out, lost by evaporation or exuded by sublimation or migration to the surface.

The polyhalopolyhydropolycyclicdicarboxylic acid or derivative, alkanolamine and dicarboxylic acid are reacted in any suitable manner and preferably when utilizing these reactants in mole proportions of l:l-2:l-2 respectively. The reaction generally is effected at a temperature above about F. and preferably at a higher temperature, which usually will not exceed about 500 F., although higher or lower temperatures may be employed under certain conditions. The exact temperature will depend upon whether a solvent is used and, when employed, on the particular solvent. For example, with benzene as the solvent, the temperature will be of the order of 175 F., with toluene the temperature will be of the order of 250 F., and with xylene in order of 300-320 F. Other solvents include cumene, naphtha, Decalin, etc. Any suitable amount of the solvent may be employed but preferably should not comprise a large excess because this will tend to lower the reaction temperature and slow the reaction. Water formed during the reaction may be removed in any suitable manner including, for example, by operating under reduced pressure, by removing an azeotrope of water-solvent, by distilling the reaction product at an elevated temperature, etc. A higher temperature may be utilized in order to remove the water as it is being formed. The time of reaction is sufficient to effect the desired condensation and, in general, will range from one-half to about 40 hours or more and preferably from about six to about 40 hours.

The reaction product will vary with the particular reactants and mole proportions thereof employed. In all cases the reaction product will comprise an ester and may include a monoester, a polyester, an imide-ester and an amide-ester or mixtures thereof.

The reaction product generally is recovered as a viscous liquid when using aliphatic substituted dibasic acids or as a solid when coreacting an unsaturated dibasic acid or derivative. I may be marketed and used as such or as a solution in a suitable solvent including, for example, saturated paraffinic hydrocarbons including pentane, hexane, heptane, octane, etc., aromatic hydrocarbons including benzene, toluene, xylene, cumene, Decalin, alcohols, ketones, etc. However, when the product is recovered in the absence of a solvent or when the product is not sufficiently soluble in the substrate, the desired solubility may be obtained by dissolving the roduct in a mutual solvent. Suitable solvents for this purpose comprise phenols and particularly alkylphenols or polyalkylphenols in which the alkyl group or groups contain from six to 20 carbon atoms. The phenol may be used in a concentration of from about percent and preferably from about 25 percent to about 500 percent by weight and, more particularly, from about 30 percent to about 200 percent by weight of the addition reaction product.

The reaction product of the present invention will have varied utility and is useful as an additive to organic substrates which undergo oxidative deterioration. The additive functions as a lubricity or extreme pressure agent and also as a flameproofing agent. In addition, the additive serves as a detergentdispersant, peroxide decomposer, corrosion inhibitor, rust inhibitor, etc. Organic substrates include gasoline, naphtha, kerosene, jet fuel, lubricating oil, diesel fuel, fuel oil, residual oil, drying oil, grease, wax, resin, plastic, rubber, etc.

The reaction product is used as an additive in lubricating oil. The lubricating oil may be of natural or synthetic origin. The mineral oils include those of petroleum origin and are referred to as motor lubricating oil, railroad type lubricating oil, marine oil, transformer oil, turbine oil, differential oil, diesel lubricating oil, gear oil, cylinder oil, specialty products oil, etc. Other oils include those of animal, marine or vegetable origin.

The lubricating oils generally have a viscosity within the range of from SUS at 100 F. to 1,000 SUS at 210 F. (SAE viscosity numbers include the range from SAE 10 to SAE 160). The petroleum oils are obtained from paraffinic, naphthenic, asphaltic or mixed base crudes. When highly paraff'mic lubricating oils are used, a solubilizing agent also is used.

Synthetic lubricating oils are of varied types including aliphatic esters, polyalkylene oxides, silicones, esters of phosphoric and silicic acids, highly fluorine-substituted hydrocarbons, etc. Of the aliphatic esters, di-(Z-ethylhexyl) sebacate is being used on a comparatively large commercial scale. Other aliphatic esters include dialkyl azelates, dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkyl glutarates. etc. Specific examples of these esters include dihexyl azelate, di-(Z-ethylhexyl) azelate, di-3,5,5-trimethylhexyl glutarate, di-3,5,5-trimethylpentyl glutarate, di-( 2-ethylhexyl) pimelate, di-( Z-ethylhexyl) adipate, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate, l,5-pentanediol-di-( 2-ethylhexanoate), etc. The polyalkylene oxides include polyisopropylene oxide, polyisopropylene oxide diether, polyisopropylene oxide diester, etc. The silicones include methyl silicone, methylphenyl silicone, etc., and the silicates include, for example, tetraisooctyl silicate, etc. The highly fluorinated hydrocarbons include fluorinated oil, perfluorohydrocarbons, etc.

Additional synthetic lubricating oils include (1) neopentyl glycol esters in which the ester group contains from three to 12 carbon atoms or more, and particularly neopentyl glycol propionates, neopentyl glycol butyrates, neopentyl glycol caproates, neopentyl glycol caprylates, neopentyl glycol pelargonates, etc., (2) trimethylol alkane esters such as the esters of trimethylol ethane, trimethylol propane, trimethylol butane, trimethylol pentane, trimethylol hexane, trimethylol heptane, trimethylol octane, trimethylol decane, trimethylol undecane, trimethylol dodecane, etc., and particularly triesters in which the ester portions each contain from three to 12 carbon atoms and may be selected from those hereinbefore specifically set forth in connection with the discussion of the neopentyl glycol esters, (3) complex esters composed of dibasic acids and glycols, especially neopentyl, neohexyl, etc., glycols further reacted or capped with monobasic acids or alcohols to give lubricants of viscosities at 210 F. of from four to 12 centistokes or higher, and (4) tricresylphosphate, trioctylphosphate, trinonylphosphate, tridecylphosphate, as well as mixed aryl and alkyl phosphates, etc.

The present invention also is used in greases made by compositing one or more thickening agents with an oil of natural or synthetic origin. Metal base synthetic greases are further classified as lithium grease, sodium grease, calcium grease, barium grease, strontium grease, aluminum grease, etc. These greases are solid or semi-solid gels and, in general, are prepared by the addition to the lubricating oil of hydrocarbon soluble metal soaps or salts of higher fatty acids, as, for example, lithium stearate, calcium stearate, aluminum naphthenate, etc. The grease may contain one or more thickening agents such as silica, carbon black, talc, organic modified Bentonite, etc., polyacrylates, amides, polyamides, aryl ureas, methyl N-n-octadecyl terephthalomate, etc. Another type of grease is prepared from oxidized petroleum wax, to which the saponifiable base is combined with the proper amount of the desired saponifying agent, and the resultant mixture is processed to produce a grease. Other types of greases in which the features of the present invention are usable include petroleum greases, whale grease, wool grease, etc., and those made from inedible fats, tallow, butcher's waste, etc.

Oils of lubricating viscosity also are used as transmission fluids, hydraulic fluids, industrial fluids, etc., and the novel features of the present invention are used to further improve the properties of these oils. During such use the lubricity pro perties of the oil are important. Any suitable lubricating oil which is used for this purpose is improved by incorporating the additive of the present invention.

Oils of lubricating viscosity also are used as cutting oils, rolling oils, soluble oils, drawing compounds, etc. In this application, the oil is used as such or as an emulsion with water. Here again, it is desired that the oil serves to lubricate the metal parts of saws, knives, blades, rollers, etc., in addition to dissipating the heat created by the contact of the moving metal pans.

Oils of lubricating viscosity also are used as slushing oils. The slushing oils are employed to protect finished or unfinished metal articles during storage or transportation from one area to another. The metal articles may be of any shape or form including steel sheets, plates, panels, coils, bars, etc., which may comprise machine parts, engines, drums, piston rings, light arms, etc., as well as farm machinery, marine equipment, parts for military or other vehicles, household equipment, factory equipment, etc. A coating which may be visible to the eye, or not, as desired, covers the metal part and protects it from corrosion, etc.

In another embodiment the reaction products of the present invention possess insecticidal properties with good innertherapautic action. They may be employed against many types of mites and insects such as, for example, Corausius larvae, Cotoneaster aphid, apple aphid, black bean aphid, aster aphid, green peach aphid, chrysanthemum aphid, pea aphid, etc. The reaction products or mixture of these may be used for the control of various larvae, mites, eggs of mites and such insects as flour beetle, mexican bean beetle, black carpet beetle, milkweed bug, german cockroaches, southern army worms, mealy bug, sow bug, citrus red spider, greenhouse red spider, various mosquitoes, yellow fever mosquito, malarial mosquito, houseflies, etc.

As hereinbefore set forth, the reaction products of the present invention also possess flame-proofing or flame retardant properties and therefore are useful in plastics, resins, coating, paints, drying oils, etc., as well as in fibrous materials. For example, in textiles, the reaction product imparts flame retardant properties to the fabric.

The plastics and resins include polyolefms such as polyethylene, polypropylene, polybutylene, etc., mixed polymers prepared from two or more of ethylene, propylene and butylene, mixed polymers of one or more each of monoolefins and diolefins, polydiolefins including polybutadiene, polystyrene, polyvinylchloride, polycarbonate, ABS (acrylonitrile-butadiene-styrene polymer), polyphenyl ethers, polyphenyl ethers modified with styrene, polyesters, polyurethanes, epoxy resins, etc.

The concentrationof the'reaction product to be'employed as an additive will depend upon the particular substrate in which it is to be used. In general, the additive is used in a concentration of from about 0.001 percent to about 25 percent by weight of the substrate and more specifically within the range of from about 0.01 percent to about percent by weight of the substrate. When used in conventional lubricating oil, the addi' tive generally may be employed in a concentration of from about 0.01 percent to about 2 percent by weight of the oil. When used in lubricating oil for more severe operations, such as hypoid gear oi], the additive is used in a concentration of from about 1 percent to about 20 percent or more by weight of the oil. In general, substantially the same range of additive concentration is employed when the oil is used as transmission fluid, hydraulic fluid, industrial fluid, etc. When the oil is used in the formulation of a grease, the additive is used in a concentration of from about 0.5 percent to 5 percent by weight of the oil. When used in cutting oil, rolling oil, soluble oil, drawing compounds, etc., the additive may be used in a concentration of from about 0.1 percent to about percent by weight ofthe oil. When used in slushing oil, the additive may be used in a concentration of from about 0.1 percent to about percent by weight or more of the oil.

It is understood that the additive of the present invention may be used along with other additives incorporated in the organic substrate. The other additives will depend upon the par ticular organic substrate. For example, in lubricating oil, the additional additives may comprise one or more of viscosity index improver, pour point depressant, anti'foam additive, detergent, corrosion inhibitor, anti-oxidant, etc. Preferred antioxidants are of the phenolic type and include tertiarybutylcatechol, 2,6-di-tertiarybutyl-4-methylphenol, 2,4-dimethyl- 6-tertiarybutylphenol, etc., 2'tertiarybutyl-4-methoxyphenol, 2-tertiary-4-ethoxyphenol, 3 ,3 ',5,5'-tetratertiarybutyl-diphenylmethane, etc.

When desired, an emulsifying agent may be employed in formulations containing the additive of the present invention. Any suitable emulsifying agent can be used, including alkali metal sulfonates of petroleum solfonic acids, mahogany sul fonates, naphthenic acids, fatty acids, etc., fatty alcohol sulfonates, pentaerythritol oleates, laurates, etc. The amount of water used in the emulsified oils will depend upon the particular use of the emulsion and may range from 0.25 percent to 50 percent or even up to 98 percent by weight of the compositlon.

The additive of the present invention is incorporated in the substrate in any suitable manner and preferably the mixture is suitably agitated or otherwise mixed in order to obtain intimate admixing of the additive and of the substrate. When the substrate comprises a mixture of two or more components, the additive of the present invention may be commingled with one of the components prior to mixing with the remaining component or components of the substrate.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

EXAMPLE I The reaction product of this example was prepared by reacting the diol corresponding to Chlorendic" acid, N-tallow-diethanolamine (Ethomeen T12) and dodecenyl succinic anhydride. The diol is prepared by reacting hexachlorocyclopentadiene with 1,4-butenediol. The polymeric reaction product is prepared by refluxing 45.13 g. (0.125 mole) of the Chlorendic diol, 48 g. (0.125 mole) of N-tallowdiethanolamine and 70.5 g. (0.25 mole) of dodecenyl succinic anhydride. The refluxing is effected at a temperature of about 340 F. for about 8 hours and a total of 4.5 cc. of water is collected. The xylene solvent is removed by distilling at a temperature up to about 350 F. under water pump vacuum. The product is recovered as a very heavy amber oil containing 16.3 percent chlorine corresponding to the theoretical content of 16.7 percent.

EXAMPLE II The reaction product of this example was prepared by reacting A" anhydride, N-tallow-diethanolamine and dodecenyl succinic anhydride. The polymeric reaction product was prepared by refluxing 53 g. (0.125 moles) ofA" anhydride, 92 g. (0.25 mole) of N-tallow-diethanolamine and 32.78 g. (0.125 moles) of dodecenyl succinic anhydride. A total of 4.5 cc. of water was collected. Following completion of the reaction, the reaction mixture was distilled under water pump vacuum to remove the xylene solvent. A 50 percent lubricating oil solution of the product was made. The reaction product solution had a basic nitrogen equivalent of 0.74 meq/g.

EXAMPLE Ill The reaction product of this example is prepared by reacting A" anhydride, N,N'-di0ctyl-N-hydroxyethylaminoethylethanolamine and polyisobutene-succinic anhydride, the polyisobutene moiety having an average molecular weight of about 1,200. The alkanolamine is prepared by the oxyethylenation of N,N'-di-octylethylenediamine. The reaction product is prepared by refluxing 1 mole proportion of the A anhydride, 2 mole proportions of the alkanolamine and 1 mole proportion of the polyisobutylene-succinic anhydride in the presence of xylene solvent. The refluxing is continued for about 10 hours and the water formed in the reaction is continuously removed. Following completion of the reaction, the reaction product is recovered in the xylene solvent and utilized in this manner as an additive for lubricating oil.

EXAMPLE IV The reaction product of this example is prepared by reacting two moles of A" anhydride, two moles of ethanolamine and one mole of maleic anhydride. The mixture is refluxed in xylene solvent with nitrogen being continuously introduced. The water formed during the reaction is continuously removed. Following completion of the reaction, the reaction product is recovered in admixture with the xylene solvent and utilized as a flame retarding coreactant.

EXAMPLE V One hundred moles of A" anhydride are reacted with moles of aminoethyl-ethanolamine in xylene. When the evolution of 200 moles of water is completed, 50 moles of polybutene substituted succinic anhydride is added and refluxed until evolution of water ceases. Mineral lubricating oil is added to make 50 percent active ingredient solution. Xylene is removed by vacuum distillation. The mineral lubricating oil solution is effective in lubricating oil as extreme pressure additive, acidity neutralizing additive corrosion inhibitor and detergent-dispersant. To further augment the extreme pressure properties, as well as the corrosion inhibiting properties of the above composition, an alkyl acid phosphate may also be incorporated in the composition.

EXAMPLE v1 One mole of l,4,5,6,7,7-hexachlorobicyclo-(2,2,l)-5-heptene-2,3-dicarboxylic acid anhydride is reacted with one mole of propanolamine. One mole of water is evolved. At the completion of water evolution, one-half mole of maleic anhydride is added and the composition is refluxed in xylene with one-half mole of water is evolved. Xylene is removed under vacuum and the remaining solid containing 45 percent chlorine is used as a flame retardant. 20 pph (parts per hundred) of the above composition together with 15 pph of antimony trioxide is cured with EPDM rubber composition to render it flame retarded.

EXAMPLE VII The reaction product of this example is prepared by reacting the ethyl ester of 8" acid (5,6,7,8,,9,9-hexachlorol,2,3,4,4a,5,8,8a octahydro-1,4,5,8-dimethano- 2,3naphthalene-dicarboxylic acid) with N-decyl-aminopropylpropanolamine and hexenyl-succinic anhydride. The ester of B acid is prepared by refluxing two mole proportions of ethyl alcohol and one mole proportion of the acid. The ester, N-decyl-aminopropyl-propanolamine and hexenyl-succinic anhydride are refluxed in the presence of xylene solvent to liberate alcohol and to form the reaction product.

EXAMPLE VIII In one embodiment the reaction products of the present invention are used as additives in lubricating oil. One method of evaluating lubricating oils is by the Falex machine. This procedure is described in detail in a book entitled Lubricant Testing" authored by E. G. Ellis and published by Scientific Publication (Great Britain) Limited, 1953, pages 150-154. Briefly, the Falex machine consists of a rotating pin which runs between two V shape bearings which are spring loaded against the pin and provided with means for varying the load. The oil to be tested is poured into a metal trough in which the pin and bearings are partly submerged. The machine is operated for 5 minutes each at 250 and 500 pound loads and then 45 minutes at 750 pound load. The data collected include the temperature of the oil at each of the loads, as well as the wear which is determined by a ratchet wheel arrangement in which the teeth are advanced in order to maintain the desired load. Each tooth is equivalent to approximately 0.000022 inches. Preferred additives are those which impart low temperature, low torque and low wear to the oil.

In another series of tests the machine is operated for five minutes at each load from 250 pounds to seizure at 250 pound increments. The maximum load and the time in minutes at this load to seizure are reported, as well as the temperature of the oil. In this case the higher temperature is preferred because it means that the oil is operating satisfactorily at a higher temperature. In one series of evaluations the lubricating oil is dioctyl sebacate synthetic lubricating oil marketed under the tradename of Plexol 201." A control sample of the lubricating oil (not containing an additive) is evaluated in the above manner and underwent seizure at a load of 750 pounds. In contrast another sample of the synthetic lubricating oil containing 2 percent by weight of the reaction product prepared as described in Example II does not undergo seizure until a load of greater than 1,200 pounds.

EXAMPLE IX Another series of evaluations is made in the same manner as described in Example VI except that the lubricating oil is a mineral oil marketed commercially as Cames 340 White Oil. When evaluated in the manner described in Example VIII, the mineral oil undergoes seizure at a load of less than500 pounds. In contrast another sample of the white oil containing 2 percent by weight of the reaction product prepared as described in Example I will not undergo seizure until a load of above 1,200 pounds is attained.

EXAMPLE VIII High temperature detergency and dispersant properties of the reaction products of the invention have been tested in ASTM-CFR (Erdco) Coker Test D-I660 using a 6 pph fuel flow. Commercial diesel fuel has been used as the testing medium. The preheater temperature has been set at 400 F. The filter temperature has been set at 932 F. The additive has been added to the fuel in a concentration of 0.001 percent by weight. The time in minutes to reach the corresponding differential (A P) of mercury pressure is reported. While the control sample of the fuel containing no additive reached the differential pressure of 25 inches of mercury in 87 minutes. 0.001 percent by weight of the additive of the present invention reduced the filter plugging considerably, as shown by the data in the following table.

The above data illustrate that the reaction product of the present invention effectively reduces filter plugging of the fuel.

EXAMPLE IX An insecticidal composition is prepared by dissolving l g. of the reaction product of Example I in 2 cc. of benzene and emulsifying the resultant solution with cc. of water using Triton X-l00 as the emulsifying agent. The resulting emulsion is sprayed into a cage containing houseflies and results in substantial knockdown.

I claim as my invention:

1. The reaction product formed by the condensation at a temperature of about F. to about 500 F. and for a time of from about one-half to about 40 hours of (a) 1 mole proportion of a polyhalopolyhydropolycyclicdicarboxylic acid to be hereinafter defined, corresponding anhydride, corresponding diol or ester of said acid, (b) 1 to 2 mole proportions of an alkanolamine to be hereinafter defined and (c) l to 2 mole proportions of a dicarboxylic acid selected from the group consisting of unsaturated C or C dicarboxylic acid or anhydride and aliphatic substituted dicarboxylic acid or anhydride having C to C carbon atoms in said acid or anhydride and containing from about two to about 80 carbon atoms in said aliphatic, said polyhalopolyhydropolycyclicdicarboxylic acid having the structural formula:

wherein X is halogen, hydrogen, or alkyl of from one to 10 carbon atoms, at least two of the Xs being halogen, Y is halogen, hydrogen or alkyl of from one to 10 carbon atoms, m is an integer of from 1 to 4, n ranges from zero to four and p ranges from 0 to 4; said alkanolamine being selected from the group consisting of monoalkanolamine containing from two to about 20 carbon atoms, N-alkyl-alkanolamine, N,N-dialkyl-alkanolamine, N-alkyl-dialkanolamine and aminoalkylalkanolamine in which each alkyl contains one to 20 carbon atoms.

2. The reaction product of claim 1 wherein said condensation is efiected for a time of from about 6 to about 40 hours.

3. The reaction product of claim 1 wherein said polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is 5,6,7,8,9,9-hexachloro-a,5,8,8a-octahydro-5,8- methano-Z,3-naphthalenedicarboxylic acid or anhydride.

4. The reaction product of claim 1 wherein said polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is 5 ,6,7,8 ,9,9-hexach1oro-a,5,8,8a-octahydrol ,4,5 ,8- dimethano-Z,B-naphthalenedicarboxylic acid or anhydride.

5. The reaction product of claim 1 wherein said polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is l,4,5,6,7,7-hexachlorodicyclo-(2.2. l )-5-heptene-2,3-dicarhoxylic acid or anhydride.

6. The reaction product of claim 1 wherein said alkanolarnine is a monoalkanolamine containing from two to about carbon atoms.

7v The reaction product of claim 1 wherein said alkanolamine is N-alkyl-dialkanolamine in which each alkyl group contains from one to 20 carbon atoms.

8. The reaction product of claim 7 wherein said a1 kanolamine is N-alkyl-diethanolamine in which each alkyl kanolamine is N-diethyl-ethanolamine.

12. The reaction product of claim 1 wherein said alkanolamine is an aminoalkyl alkanolamine.

13. The reaction product of claim 12 wherein said alkanolamine is an aminoethyl ethanolarnine.

14. The reaction product of claim 12 wherein said alkanolarnine is N,N-dia]kyl-aminoethyl-ethanolamine in which said alkyl groups contain from one to 20 carbon atoms each.

15. The reaction product of claim 1 wherein the aliphatic dicarboxylic acid anhydride is alkenyl-acid anhydride.

16. The reaction product of claim 16 wherein said alkenylacid anhydride is dodecenyl-succinic anhydride.

17. The reaction product of claim 1 wherein the aliphatic substituted dicarboxylic acid contains from 40 to carbon atoms in said aliphatic.

18. The reaction product of claim 17 wherein said alkenylacid anhydride is a polyolefin-acid anhydride.

19. The reaction product of claim 18 wherein the alkenylacid anhydride is polyisobutylene-succinic anhydride.

20. The reaction product of claim 1 wherein the acid anhydride is maleic anhydride. 

2. The reaction product of claim 1 wherein said condensation is effected for a time of from about 6 to about 40 hours.
 3. The reaction product of claim 1 wherein said polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is 5,6, 7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3 -naphthalenedicarboxylic acid or anhydride.
 4. The reaction product of claim 1 wherein said polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is 5,6, 7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-1,4,5,8-dimethano-2,3 -naphthalenedicarboxylic acid or anhydride.
 5. The reaction producT of claim 1 wherein said polyhalopolyhydropolycyclicdicarboxylic acid or anhydride is 1,4, 5,6,7,7-hexachlorodicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid or anhydride.
 6. The reaction product of claim 1 wherein said alkanolamine is a monoalkanolamine containing from two to about 20 carbon atoms.
 7. The reaction product of claim 1 wherein said alkanolamine is N-alkyl-dialkanolamine in which each alkyl group contains from one to 20 carbon atoms.
 8. The reaction product of claim 7 wherein said alkanolamine is N-alkyl-diethanolamine in which each alkyl group contains from one to 20 carbon atoms.
 9. The reaction product of claim 8 wherein said alkanolamine is N-tallow-diethanolamine.
 10. The reaction product of claim 1 wherein said alkanolamine is N-dialkyl-alkanolamine in which said alkyl groups contain from one to 20 carbon atoms each.
 11. The reaction product of claim 10 wherein said alkanolamine is N-diethyl-ethanolamine.
 12. The reaction product of claim 1 wherein said alkanolamine is an aminoalkyl alkanolamine.
 13. The reaction product of claim 12 wherein said alkanolamine is an aminoethyl ethanolamine.
 14. The reaction product of claim 12 wherein said alkanolamine is N,N''-dialkyl-aminoethyl-ethanolamine in which said alkyl groups contain from one to 20 carbon atoms each.
 15. The reaction product of claim 1 wherein the aliphatic dicarboxylic acid anhydride is alkenyl-acid anhydride.
 16. The reaction product of claim 16 wherein said alkenyl-acid anhydride is dodecenyl-succinic anhydride.
 17. The reaction product of claim 1 wherein the aliphatic substituted dicarboxylic acid contains from 40 to 80 carbon atoms in said aliphatic.
 18. The reaction product of claim 17 wherein said alkenyl-acid anhydride is a polyolefin-acid anhydride.
 19. The reaction product of claim 18 wherein the alkenyl-acid anhydride is polyisobutylene-succinic anhydride.
 20. The reaction product of claim 1 wherein the acid anhydride is maleic anhydride. 